JPS6220215B2 - - Google Patents
Info
- Publication number
- JPS6220215B2 JPS6220215B2 JP58148665A JP14866583A JPS6220215B2 JP S6220215 B2 JPS6220215 B2 JP S6220215B2 JP 58148665 A JP58148665 A JP 58148665A JP 14866583 A JP14866583 A JP 14866583A JP S6220215 B2 JPS6220215 B2 JP S6220215B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- particulate polymer
- dispersion stabilizer
- producing
- polyisocyanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920000642 polymer Polymers 0.000 claims description 94
- 239000006185 dispersion Substances 0.000 claims description 55
- 239000003381 stabilizer Substances 0.000 claims description 46
- 239000002253 acid Substances 0.000 claims description 44
- 239000005056 polyisocyanate Substances 0.000 claims description 40
- 229920001228 polyisocyanate Polymers 0.000 claims description 40
- 125000004018 acid anhydride group Chemical group 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 21
- -1 alicyclic hydrocarbon Chemical class 0.000 claims description 20
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 11
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 9
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 8
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 8
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical group CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 8
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims description 7
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 3
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- HENCHDCLZDQGIQ-UHFFFAOYSA-N 3-[3,5-bis(2-carboxyethyl)-2,4,6-trioxo-1,3,5-triazinan-1-yl]propanoic acid Chemical compound OC(=O)CCN1C(=O)N(CCC(O)=O)C(=O)N(CCC(O)=O)C1=O HENCHDCLZDQGIQ-UHFFFAOYSA-N 0.000 claims description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 2
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 claims description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229920005604 random copolymer Polymers 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 32
- 239000000243 solution Substances 0.000 description 27
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 21
- 239000002245 particle Substances 0.000 description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 19
- 238000003756 stirring Methods 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 229910001873 dinitrogen Inorganic materials 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 125000000524 functional group Chemical group 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 229920002554 vinyl polymer Polymers 0.000 description 10
- 239000000178 monomer Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 8
- 239000004642 Polyimide Substances 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 8
- 229920001721 polyimide Polymers 0.000 description 8
- 239000004342 Benzoyl peroxide Substances 0.000 description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000004962 Polyamide-imide Substances 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 229920001568 phenolic resin Polymers 0.000 description 6
- 229920002312 polyamide-imide Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 125000005462 imide group Chemical group 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000013638 trimer Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 229920003180 amino resin Polymers 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- IWTIBPIVCKUAHK-UHFFFAOYSA-N 3-[bis(2-carboxyethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CCC(O)=O)CCC(O)=O IWTIBPIVCKUAHK-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical class O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 229940057995 liquid paraffin Drugs 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 2
- 229920003055 poly(ester-imide) Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- UFMBOFGKHIXOTA-UHFFFAOYSA-N 2-methylterephthalic acid Chemical compound CC1=CC(C(O)=O)=CC=C1C(O)=O UFMBOFGKHIXOTA-UHFFFAOYSA-N 0.000 description 1
- XGJZQNMUVTZITK-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexamethoxy-1,3,5-triazine-2,4,6-triamine Chemical compound CON(OC)C1=NC(N(OC)OC)=NC(N(OC)OC)=N1 XGJZQNMUVTZITK-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- MPJGGYGWCMNTKP-UHFFFAOYSA-N 3-(2,5-dioxooxolan-3-yl)propanoic acid Chemical compound OC(=O)CCC1CC(=O)OC1=O MPJGGYGWCMNTKP-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- AIVVXPSKEVWKMY-UHFFFAOYSA-N 4-(3,4-dicarboxyphenoxy)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 AIVVXPSKEVWKMY-UHFFFAOYSA-N 0.000 description 1
- MQAHXEQUBNDFGI-UHFFFAOYSA-N 5-[4-[2-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenyl]propan-2-yl]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)C(C)(C=2C=CC(OC=3C=C4C(=O)OC(=O)C4=CC=3)=CC=2)C)=C1 MQAHXEQUBNDFGI-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 1
- STZIXLPVKZUAMV-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1(C(O)=O)C(O)=O STZIXLPVKZUAMV-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- AIJZIRPGCQPZSL-UHFFFAOYSA-N ethylenetetracarboxylic acid Chemical compound OC(=O)C(C(O)=O)=C(C(O)=O)C(O)=O AIJZIRPGCQPZSL-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical class O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- MSYLJRIXVZCQHW-UHFFFAOYSA-N formaldehyde;6-phenyl-1,3,5-triazine-2,4-diamine Chemical class O=C.NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 MSYLJRIXVZCQHW-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- OBKARQMATMRWQZ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 OBKARQMATMRWQZ-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- FVDOBFPYBSDRKH-UHFFFAOYSA-N perylene-3,4,9,10-tetracarboxylic acid Chemical compound C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=O)C2=C1C3=CC=C2C(=O)O FVDOBFPYBSDRKH-UHFFFAOYSA-N 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- RTHVZRHBNXZKKB-UHFFFAOYSA-N pyrazine-2,3,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=NC(C(O)=O)=C(C(O)=O)N=C1C(O)=O RTHVZRHBNXZKKB-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
- C08G18/0871—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1035—Preparatory processes from tetracarboxylic acids or derivatives and diisocyanates
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
【発明の詳細な説明】
本発明は粒子状重合体の製造法に関し、さらに
詳しくは主にシート、成形モールド品、接着剤、
塗料、複合材料などに適用しうる耐熱性にすぐれ
た粒子状重合体の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing particulate polymers, and more particularly, mainly to sheets, molded products, adhesives,
This article relates to a method for producing particulate polymers with excellent heat resistance that can be applied to paints, composite materials, etc.
ポリイソシアネートと酸無水物基を有するポリ
カルボン酸とをＮ−メチルピロリドン、ジメチル
フオルムアミド、ジメチルアセトアミドなどの高
価な溶媒中で溶液状で反応させて、イミド基を有
する重合体溶液、例えばポリアミドイミド溶液、
ポリイミド溶液などを得ることが知られている。
しかしながら、かかる重合体溶液から固体重合体
を得るためには極めて不経済なプロセスによる溶
媒の除去又は回収操作が必要であり、工業的規模
の製造においてコスト的に大きな問題がある。固
体重合体を得るための有力な一つの製法は溶媒を
必要としない塊状重合法である。しかしながら、
イミド基を有する重合体は一般に剛直で高極性の
分子構造をもち、高いガラス転移温度によつて特
徴づけられる。従つて、塊状重合法の適用にあた
つては、一般に高温、高圧の過酷な条件下で反応
を進める必要があるため、反応の制御、副反応の
抑制などが困難であり、未だ実用化に成功した例
は見当らない。 A polyisocyanate and a polycarboxylic acid having an acid anhydride group are reacted in a solution state in an expensive solvent such as N-methylpyrrolidone, dimethylformamide, or dimethylacetamide to produce a polymer solution having an imide group, such as polyamideimide. solution,
It is known to obtain polyimide solutions and the like.
However, in order to obtain a solid polymer from such a polymer solution, it is necessary to remove or recover the solvent by an extremely uneconomical process, which poses a major cost problem in industrial scale production. One promising method for obtaining solid polymers is a bulk polymerization method that does not require a solvent. however,
Polymers having imide groups generally have a rigid and highly polar molecular structure and are characterized by a high glass transition temperature. Therefore, when applying the bulk polymerization method, it is generally necessary to proceed with the reaction under harsh conditions of high temperature and high pressure, making it difficult to control the reaction and suppress side reactions, and it is still difficult to put into practical use. There are no successful examples.
又、ポリアミド樹脂の中では芳香族ポリアミド
が非常に耐熱性が良いと知られているが、一般的
に芳香族ジカルボン酸と芳香族ジアミンとの反応
性は充分でない。６・６−ナイロンや６−ナイロ
ンのような高分子量の重合体を得るためには、遊
離のカルボン酸より反応性に富む芳香族ジカルボ
ン酸二塩化物と芳香族ジアミンの重合反応が用い
られる。しかし、芳香族ジアミンと芳香族ジカル
ボン酸二塩化物の反応では塩酸が副生し、好まし
くないアミン塩酸塩が生成するなどの副反応を起
こすので塩酸を除去する必要があり、工業的規模
の製造では問題を残している。 Furthermore, among polyamide resins, aromatic polyamides are known to have very good heat resistance, but generally the reactivity between aromatic dicarboxylic acids and aromatic diamines is not sufficient. In order to obtain high molecular weight polymers such as 6,6-nylon and 6-nylon, a polymerization reaction of aromatic dicarboxylic acid dichloride, which is more reactive than free carboxylic acid, and aromatic diamine is used. However, in the reaction of aromatic diamine and aromatic dicarboxylic acid dichloride, hydrochloric acid is produced as a by-product, and side reactions such as formation of undesirable amine hydrochloride occur, so it is necessary to remove the hydrochloric acid, which requires industrial-scale production. That leaves a problem.
本発明者らは、耐熱性のすぐれた粒子状重合体
のこのような欠点の改良された安価な製造法につ
いて検討を重ねた結果、非水有機液体中に分散さ
れた粒子状重合体の製造法を完成するに至つた。
すなわち本発明は、生成する粒子状重合体に対し
て不溶性である非水有機液体及び非水有機液体に
可溶な分散安定剤の存在下で、ポリイソシアネー
ト（）と酸無水物基を有するポリカルボン酸
（）及び／又はポリカルボン酸（）とを反応
させて、非水有機液体中に分散された粒子状重合
体とするイミド基を有する粒子状重合体の製造法
に関する。 As a result of repeated studies on an inexpensive manufacturing method for particulate polymers with excellent heat resistance that overcomes these drawbacks, the present inventors have developed a method for producing particulate polymers dispersed in non-aqueous organic liquids. He has completed the Dharma.
That is, the present invention provides a method for preparing a polyisocyanate () and a polyester having an acid anhydride group in the presence of a non-aqueous organic liquid that is insoluble in the particulate polymer to be produced and a dispersion stabilizer that is soluble in the non-aqueous organic liquid. The present invention relates to a method for producing a particulate polymer having an imide group by reacting with a carboxylic acid () and/or a polycarboxylic acid () to obtain a particulate polymer dispersed in a non-aqueous organic liquid.
本発明の製造法によれば、粒子状重合体は、非
水有機液体中で比較的小さな粒子の分散体として
得られるため過操作によつて容易に分散体から
回収できる。また、特に本発明になる製造法では
非水有機液体として、生成する粒子状重合体に対
して不溶性である安価な汎用溶媒を用いることが
できる。重合体の溶媒に対する不溶性によつて高
固形分化に限界がある溶液重合法と違つて、本発
明によれば非水有機液体中で50重量％以上の高固
形分を得ることができる。 According to the production method of the present invention, the particulate polymer is obtained as a dispersion of relatively small particles in a non-aqueous organic liquid and can therefore be easily recovered from the dispersion by over-operation. Furthermore, particularly in the production method of the present invention, an inexpensive general-purpose solvent that is insoluble in the particulate polymer to be produced can be used as the non-aqueous organic liquid. Unlike solution polymerization methods, which have a limit to high solid content due to the insolubility of the polymer in solvents, the present invention makes it possible to obtain high solid content of 50% by weight or more in non-aqueous organic liquids.
また、本発明における粒子状重合体への単量体
の転換率は溶液重合法における反応温度領域で十
分に高めることができ、比較的温和な条件下で反
応を完結できるため副反応などによる純度の低下
をきたさない。 In addition, the conversion rate of monomers into particulate polymers in the present invention can be sufficiently increased in the reaction temperature range of solution polymerization, and the reaction can be completed under relatively mild conditions, resulting in purity due to side reactions etc. does not cause a decrease in
本発明における非水有機液体としては、生成す
る粒子状重合体に対して不溶性であつて、重合反
応を阻害しない不溶性な性質を有する非水有機液
体が用いられる。 As the non-aqueous organic liquid in the present invention, a non-aqueous organic liquid is used that is insoluble in the particulate polymer to be produced and has an insoluble property that does not inhibit the polymerization reaction.
例えばｎ−ヘキサン、オクタン、ドデカン、
ISOPAR−Ｅ、ISOPAR−Ｈ、ISOPAR−Ｋ、
ISOPAR−Ｌ、ISOPAR−Ｍ（以上、エツソ・ス
タンダード石油社製商品名。沸点範囲が40〜300
℃程度の石油系飽和脂肪族又は脂肪族炭化水素）
等の脂肪族又は脂肪族炭化水素類、ベンゼン、ト
ルエン、キシレン、NISSEKI HISOL−100、
NISSEKI HISOL−150（以上、日本石油化学社
製商品名。沸点範囲が80〜300℃程度の石油系芳
香族炭化水素）等の芳香族脂肪族類などが用いら
れる。反応温度を考慮すると沸点が80℃以上のも
のが好ましい。これらは単独で又は二種以上を用
いることができる。 For example, n-hexane, octane, dodecane,
ISOPAR-E, ISOPAR-H, ISOPAR-K,
ISOPAR-L, ISOPAR-M (these are product names manufactured by Etsuso Standard Oil Co., Ltd. Boiling point range is 40 to 300
(petroleum-based saturated aliphatic or aliphatic hydrocarbons)
Aliphatic or aliphatic hydrocarbons such as benzene, toluene, xylene, NISSEKI HISOL-100,
Aromatic aliphatics such as NISSEKI HISOL-150 (trade name manufactured by Nippon Petrochemical Co., Ltd.; a petroleum-based aromatic hydrocarbon with a boiling point range of about 80 to 300°C) are used. Considering the reaction temperature, those having a boiling point of 80°C or higher are preferred. These can be used alone or in combination of two or more.
本発明に用いられる分散安定剤は、上記の非水
有機液体に不溶性であつて、生成する粒子状重合
体の表面にあつて安定化層を形成し、少なくとも
重合過程における粒子の分散状態を安定化する働
きを有するものであれば使用でき、特に制限はな
い。このような分散安定剤としては、例えば分散
相となる重合体又は重合体を形成する反応剤溶液
（ポリイソシアネートと酸無水物基を有するポリ
カルボン酸及び／又はポリカルボン酸とから形成
される溶液）に対して親和性を有する第一の有機
成分と連続相となる非水有機液体に可溶性の第二
の有機成分とを共有する樹脂が用いられる。 The dispersion stabilizer used in the present invention is insoluble in the above-mentioned non-aqueous organic liquid, forms a stabilizing layer on the surface of the particulate polymer to be produced, and stabilizes the dispersion state of the particles at least during the polymerization process. Any material can be used as long as it has the function of oxidizing, and there are no particular restrictions. Examples of such a dispersion stabilizer include, for example, a polymer serving as a dispersed phase or a reactant solution forming a polymer (a solution formed from a polyisocyanate and a polycarboxylic acid and/or polycarboxylic acid having an acid anhydride group). ) and a second organic component soluble in a non-aqueous organic liquid serving as a continuous phase are used.
分散相に対して親和性である第一の有機成分と
してはエーテル基、エステル基、アミド基、イミ
ド基などの極性結合基を介してなる主に芳香族系
鎖状重合体、例えばテレフタル酸又はイソフタル
酸と２価アルコールとから得られる鎖状ポリエス
テル、ポリアミド、ポリアミドイミド、ポリイミ
ド、ポリエーテルアミド、ポリエステルアミド、
ポリエステルアミドイミド、ポリエステルイミ
ド、ビスフエノール型エポキシ樹脂、極性基を有
するビニル単量体、例えばアクリロニトリル、ア
クリルアミド、ビニルピロリドン、ビニルピリジ
ン、ビニルラクタム等の重合体又は共重合体など
が用いられる。連続相（非水有機液体）に可溶性
の第二の有機成分としては極性の低い主として脂
肪族系鎖状重合体が用いられる。例えば、アクリ
ル酸又はメタクリル酸のブチル、ヘキシル、２−
メチルヘキシル、オクチル、ラウリル又はステア
リルエステルの重合体又は共重合体、重合度が３
〜100のポリエチレンオキシドのモノアルコキシ
ド体、重合度が３〜100のポリプロピレンオキシ
ドのモノアルコキシド体及びそのモノメタクリレ
ート、例えばNKエステルＭ−9G、Ｍ−23G（以
上新中村化学社製、商品名）の重合体又は共重合
体、ポリブタジエン、ポリイソプレン等のビニル
重合体、分子量が1000以上のポリヒドロキシ脂肪
酸エステルの片末端封鎖体、例えば12−ヒドロキ
システアリン酸の自己縮合体の１価カルボン酸又
は１価アルコールによる片末端封鎖体及びそのグ
リシジルメタクリレート付加物の重合体又は共重
合体、分解天然ゴム、セルロース誘導体などが用
いられる。 The first organic component having an affinity for the dispersed phase is mainly an aromatic chain polymer formed through a polar bonding group such as an ether group, an ester group, an amide group, or an imide group, such as terephthalic acid or Chain polyester, polyamide, polyamideimide, polyimide, polyetheramide, polyesteramide obtained from isophthalic acid and dihydric alcohol,
Polyester amide imide, polyester imide, bisphenol type epoxy resin, vinyl monomers having polar groups, such as polymers or copolymers of acrylonitrile, acrylamide, vinyl pyrrolidone, vinyl pyridine, vinyl lactam, etc. are used. As the second organic component soluble in the continuous phase (non-aqueous organic liquid), a mainly aliphatic chain polymer with low polarity is used. For example, butyl, hexyl, 2-acrylic or methacrylic acid
Polymer or copolymer of methylhexyl, octyl, lauryl or stearyl ester, with a degree of polymerization of 3
~100 monoalkoxide of polyethylene oxide, monoalkoxide of polypropylene oxide with a polymerization degree of 3 to 100, and its monomethacrylate, such as NK ester M-9G, M-23G (manufactured by Shin Nakamura Chemical Co., Ltd., trade name). Polymers or copolymers, vinyl polymers such as polybutadiene and polyisoprene, single-end-blocked products of polyhydroxy fatty acid esters with a molecular weight of 1000 or more, monovalent carboxylic acids or monovalent self-condensates of 12-hydroxystearic acid, etc. Polymers or copolymers of one end-capped product with alcohol and its glycidyl methacrylate adduct, decomposed natural rubber, cellulose derivatives, and the like are used.
これらの第一の有機成分と第二の有機成分とは
化学的結合を介して連結したランダム重合体、ブ
ロツク重合体又はグラフト重合体として得られ
る。 The first organic component and the second organic component are obtained as a random polymer, block polymer, or graft polymer linked through chemical bonds.
分散安定剤として用いられる他の例は、反応剤
（ポリイソシアネート、酸無水物基を有するポリ
カルボン酸及び／又はポリカルボン酸、以下同
じ）が有するイソシアネート基、酸無水物基又は
カルボキシル基のいずれかと反応しうる１種又は
２種以上の官能基を有する樹脂が用いられる。こ
のような官能基としては、例えばイソシアネート
基に対してはヒドロキシル基、カルボキシル基、
メチロール基、アミノ基、酸無水物基、エポキシ
基などがある。好ましくはヒドロキシル基又はエ
ポキシ基が用いられる。酸無水物基及びカルボキ
シル基に対しては、例えばイソシアネート基、ヒ
ドロキシル基、アミノ基、エポキシ基などがあ
る。官能基としてはヒドロキシル基又はエポキシ
基が好ましい。このような官能基を有する樹脂と
しては、例えばブチル化ベンゾグアナミンホルム
アルデヒド樹脂、ブチル化メラミンホルムアルデ
ヒド樹脂等のアルコキシ変性アミノ樹脂、ヒドロ
キシル基、カルボキシル基、酸無水物基、エポキ
シ基、イソシアネート基、メルカプタン基等を有
する平均分子量数千程度のテレキーリツクゴム、
分解天然ゴムなどが用いられる。また、分散安定
剤として、前記の第一の有機成分と第二の有機成
分とが化学的結合を介して連結したランダム重合
体、ブロツク重合体又はグラフト重合体の前記の
第一の有機成分に官能基を導入したものが用いら
れる。また前記した連続相（非水有機液体）に可
溶性の前記の第二の有機成分に官能基を導入した
ものなどが用いられる。これらの樹脂への官能基
の導入方法は分散安定剤がビニル重合体の場合、
官能基を有するビニルモノマーを共重合させれば
よい。ヒドロキシル基を有するビニルモノマーと
しては、例えばアリルアルコール、アクリル酸又
はメタクリル酸のヒドロキシエチル又はヒドロキ
シプロピルエステル、重合度３〜100のポリエチ
レンオキシド又は重合度３〜100のポリプロピレ
ンオキシドのアクリル酸又はメタクリル酸エステ
ルなどが用いられる。カルボキシル基を有するビ
ニルモノマーとしては、例えばアクリル酸、メタ
クリル酸、イタコン酸などが用いられる。酸無水
物基を有するビニルモノマーとしては、例えば無
水マレイン酸、無水イタコン酸などが用いられ
る。エポキシ基を有するビニルモノマーとして
は、例えばアクリル酸又はメタクリル酸のグリシ
ジルエステル又はアリールグリシジルエステルな
どが用いられる。メチロール基を有するビニルモ
ノマーとしては、メチロールアクリルアミドなど
が用いられる。 Other examples of dispersion stabilizers used include any isocyanate group, acid anhydride group, or carboxyl group possessed by the reactant (polyisocyanate, polycarboxylic acid and/or polycarboxylic acid having an acid anhydride group, the same applies hereinafter). A resin having one or more functional groups capable of reacting with ions is used. Such functional groups include, for example, hydroxyl group, carboxyl group,
Examples include methylol group, amino group, acid anhydride group, and epoxy group. Preferably hydroxyl or epoxy groups are used. Examples of acid anhydride groups and carboxyl groups include isocyanate groups, hydroxyl groups, amino groups, and epoxy groups. The functional group is preferably a hydroxyl group or an epoxy group. Examples of resins having such functional groups include alkoxy-modified amino resins such as butylated benzoguanamine formaldehyde resins and butylated melamine formaldehyde resins, hydroxyl groups, carboxyl groups, acid anhydride groups, epoxy groups, isocyanate groups, mercaptan groups, etc. Telekey rubber with an average molecular weight of several thousand,
Decomposed natural rubber is used. In addition, as a dispersion stabilizer, the first organic component of a random polymer, block polymer, or graft polymer in which the first organic component and the second organic component are linked through a chemical bond can be used as a dispersion stabilizer. Those into which functional groups are introduced are used. Also used are those in which a functional group is introduced into the second organic component that is soluble in the continuous phase (non-aqueous organic liquid). When the dispersion stabilizer is a vinyl polymer, the method for introducing functional groups into these resins is as follows:
What is necessary is to copolymerize a vinyl monomer having a functional group. Examples of the vinyl monomer having a hydroxyl group include allyl alcohol, hydroxyethyl or hydroxypropyl ester of acrylic acid or methacrylic acid, polyethylene oxide with a degree of polymerization of 3 to 100, or acrylic acid or methacrylate of polypropylene oxide with a degree of polymerization of 3 to 100. etc. are used. As the vinyl monomer having a carboxyl group, for example, acrylic acid, methacrylic acid, itaconic acid, etc. are used. As the vinyl monomer having an acid anhydride group, for example, maleic anhydride, itaconic anhydride, etc. are used. As the vinyl monomer having an epoxy group, for example, glycidyl ester or arylglycidyl ester of acrylic acid or methacrylic acid is used. As the vinyl monomer having a methylol group, methylol acrylamide or the like is used.
付加重合体、縮合重合体の場合は重合体を形成
するモノマーが有する官能基又は反応によつて生
ずる官能基を重合体末端に残存させることによつ
て容易に導入できる。ポリエチレンオキシド、ポ
リプロピレンオキシドなどの場合にはヒドロキシ
ル基を残存させることができる。ポリカルボン酸
又はその無水物とポリアルコールとから得られる
ポリエステルの場合にはカルボキシル基、酸無水
物基又はヒドロキシル基を残存させることができ
る。ポリカルボン酸又はその酸無水物とポリイソ
シアネート又はポリアミンとから得られるポリア
ミド、ポリイミド又はポリアミドイミドの場合に
はカルボキシル基、酸無水物基、イソシアネート
基、アミノ基などを残存させることができる。 In the case of addition polymers and condensation polymers, it can be easily introduced by leaving a functional group possessed by the monomer forming the polymer or a functional group generated by reaction at the end of the polymer. In the case of polyethylene oxide, polypropylene oxide, etc., hydroxyl groups can remain. In the case of polyesters obtained from polycarboxylic acids or their anhydrides and polyalcohols, carboxyl groups, acid anhydride groups, or hydroxyl groups may remain. In the case of polyamide, polyimide or polyamideimide obtained from polycarboxylic acid or its acid anhydride and polyisocyanate or polyamine, carboxyl groups, acid anhydride groups, isocyanate groups, amino groups, etc. may remain.
分散安定剤としては、ラウリルメタクリレー
ト、ステアリルメタクリレート、ラウリルアクリ
レート又はステアリルアクリレートとメタクリル
酸−２−ヒドロキシエチル、メタクリル酸グリシ
ジル、アクリル酸−２−ヒドロキシエチル及び／
又はアクリル酸グリシジルとのランダム共重合体
が好ましい。 As the dispersion stabilizer, lauryl methacrylate, stearyl methacrylate, lauryl acrylate or stearyl acrylate and 2-hydroxyethyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate and/or
Or a random copolymer with glycidyl acrylate is preferred.
分散安定剤の製造法には特に制限はなく、例え
ば非水有機液体中でラジカル重合によつて得られ
る。 There are no particular restrictions on the method for producing the dispersion stabilizer, and it can be obtained, for example, by radical polymerization in a non-aqueous organic liquid.
分散安定剤の数平均分子量は600以上であるこ
とが好ましい。安定性、取扱い易さを考慮すると
数平均分子量が6000〜300000の範囲が更に好まし
いとされる。 The number average molecular weight of the dispersion stabilizer is preferably 600 or more. Considering stability and ease of handling, it is said that a number average molecular weight in the range of 6,000 to 300,000 is more preferable.
数平均分子量は分子量既知のポリスチレンを検
量線とするゲルパーミエーシヨンクロマトグラフ
イ法から求められる。 The number average molecular weight is determined by gel permeation chromatography using polystyrene of known molecular weight as a calibration curve.
分散安定剤の数平均分子量は、例えばラジカル
重合では製造の際の反応温度と触媒量によつて調
節される。 The number average molecular weight of the dispersion stabilizer is controlled, for example, in radical polymerization by the reaction temperature and catalyst amount during production.
分散安定剤中に前記した官能基を含有させる場
合には、官能基を有する第一の有機成分(A)と第二
の有機成分(B)の反応モル比(B)／(A)が１／１〜５／
１の範囲が好ましい。反応モル比(B)／(A)が５／１
を越えると分散安定剤は生成する粒子状重合体と
結合できない結果、粒子状重合体の粒子表面に安
定化層を形成できず、凝集を起こし易くなる。ま
た、反応モル比(B)／(A)が１／１未満では生成する
粒子状重合体が好ましくないゲル化を生ずること
がある。 When the above-mentioned functional group is contained in the dispersion stabilizer, the reaction molar ratio (B)/(A) of the first organic component (A) having the functional group and the second organic component (B) is 1. /1~5/
A range of 1 is preferred. Reaction molar ratio (B)/(A) is 5/1
If it exceeds this amount, the dispersion stabilizer cannot bond with the particulate polymer to be produced, and as a result, a stabilizing layer cannot be formed on the particle surface of the particulate polymer, which tends to cause aggregation. Furthermore, if the reaction molar ratio (B)/(A) is less than 1/1, the resulting particulate polymer may undergo undesirable gelation.
本発明に用いられるポリイソシアネートとして
は、例えばトリレンジイソシアネート、キシリレ
ンジイソシアネート、４・4′−ジフエニルエーテ
ルジイソシアネート、ナフタレン−１・５−ジイ
ソシアネート、４・4′−ジフエニルメタンジイソ
シアネート等の芳香族ジイソシアネート、エチレ
ンジイソシアネート、１・４−テトラメチレンジ
イソシアネート、１・６−ヘキサメチレンジイソ
シアネート、１・12−ドデカンジイソシアネート
等の脂肪族ジイソシアネート、シクロブテン１・
３−ジイソシアネート、シクロヘキサン１・３−
および１・４−ジイソシアネート、イソフオロン
ジイソシアネート等の脂環式ジイソシアネート、
トリフエニルメタン−４・4′・4″−トリイソシア
ネート、ポリフエニルメチルポリイソシアネー
ト、例えばアニリンとフオルムアルデヒドとの縮
合物とフオスゲン化したもの等のポリイソシアネ
ート、これらのポリイソシアネートの三量化反応
によつて得られるイソシアヌレート環含有ポリイ
ソシアネートが使用される。耐熱性、コスト面等
を考慮すると、トリレンジイソシアネート、４・
4′−ジフエニルメタンジイソシアネート、４・
4′−ジフエニルエーテルジイソシアネート、トリ
フエニル−４・4′・4″−トリイソシアネートなど
の芳香族ポリイソシアネート及びこれらの芳香族
ジイソシアネートの三量化反応によつて得られる
イソシアヌレート環含有ポリイソシアネートを用
いることが好ましい。イソシアヌレート環含有ポ
リイソシアネートの製造法は特公昭56−34209号
公報に示されている。イソシアヌレート環含有ポ
リイソシアネートは分岐成分として使用され、そ
のイソシアヌレート環骨核はすぐれた耐熱性を付
与する。実質的に線状であつて熱可塑性であるイ
ミド基を有する粒子状重合体の合成には二官能性
のポリイソシアネートが使用される。また、分岐
した熱硬化性のイミド基を有する粒子状重合体の
合成には三官能性以上のポリイソシアネートが使
用される。これらポリイソシアネートは目的に応
じて単独又は混合して用いられる。ポリイソシア
ネートは重縮合反応過程での反応速度を制御し、
安定な粒子状重合体を得るためにメタノール、ｎ
−ブタノール、ベンジルアルコール、ε−カプロ
ラクタム、メチルエチルケトンオキシム、フエノ
ール、クレゾールなどの活性水素を分子内に１個
有する適当なブロツク剤で一部分又は全部を安定
化したものを使用してもよい。 Examples of the polyisocyanates used in the present invention include aromatic polyisocyanates such as tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, naphthalene-1,5-diisocyanate, and 4,4'-diphenylmethane diisocyanate. Aliphatic diisocyanates such as diisocyanate, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutene 1.
3-diisocyanate, cyclohexane 1,3-
and cycloaliphatic diisocyanates such as 1,4-diisocyanate and isophorone diisocyanate,
Triphenylmethane-4,4',4''-triisocyanate, polyphenylmethyl polyisocyanate, polyisocyanates such as phosgenated condensates of aniline and formaldehyde, and trimerization reactions of these polyisocyanates. The resulting isocyanurate ring-containing polyisocyanate is used. Considering heat resistance, cost, etc., tolylene diisocyanate, 4.
4'-diphenylmethane diisocyanate, 4.
Use of aromatic polyisocyanates such as 4'-diphenyl ether diisocyanate and triphenyl-4,4',4''-triisocyanate, and isocyanurate ring-containing polyisocyanates obtained by trimerization reaction of these aromatic diisocyanates. is preferred.A method for producing isocyanurate ring-containing polyisocyanates is disclosed in Japanese Patent Publication No. 56-34209.Isocyanurate ring-containing polyisocyanates are used as branching components, and the isocyanurate ring core has excellent heat resistance. Difunctional polyisocyanates are used in the synthesis of particulate polymers with substantially linear and thermoplastic imide groups. Trifunctional or higher-functionality polyisocyanates are used to synthesize particulate polymers with polyisocyanates.These polyisocyanates can be used alone or in combination depending on the purpose.Polyisocyanates control the reaction rate during the polycondensation reaction process. death,
Methanol, n to obtain a stable particulate polymer
It is also possible to use a compound partially or entirely stabilized with a suitable blocking agent having one active hydrogen in the molecule, such as -butanol, benzyl alcohol, ε-caprolactam, methyl ethyl ketone oxime, phenol, and cresol.
酸無水物基を有するポリカルボン酸としては、
例えばトリメリツト酸無水物、１・２・４−ブタ
ントリカルボン酸−１・２−無水物、３・４・
4′−ベンゾフエノントリカルボン酸−３・4′−無
水物等のトリカルボン酸無水物、１・２・３・４
−ブタンテトラカルボン酸、シクロペンタンテト
ラカルボン酸、エチレンテトラカルボン酸、ビシ
クロ−〔２・２・２〕−オクト−(7)−エン−２：
３・５：６−テトラカルボン酸等の脂肪族系およ
び脂環族系四塩基酸、ピロメリツト酸、３・3′・
４・4′−ベンゾフエノンテトラカルボン酸、ビス
（３・４−ジカルボキシフエニル）エーテル、
２・３・６・７−ナフタレンテトラカルボン酸、
１・２・５・６−ナフタレンテトラカルボン酸、
エチレングリコールビストリメリテート、２・
2′−ビス（３・４−ビスカルボキシフエニル）プ
ロパン、２・2′・３・3′−、又は３・3′・４・
4′−ビスフエニルテトラカルボン酸、ペリレン−
３・４・９・10−テトラカルボン酸、ビス３・４
−ジカルボキシフエニルスルホン、２・２−ビス
〔４−（２・３−、又は３・４−ジカルボキシフエ
ノキシ）フエニル〕プロパン、４−（２・３−ジ
カルボキシフエノキシ）−4′−（３・４−ジカルボ
キシフエノキシ）−ジフエニル−２・２−プロパ
ン等の芳香族四塩基酸、チオフエン−２・３・
４・５−テトラカルボン酸、ピラジンテトラカル
ボン酸等の複素環式四塩基酸などの四塩基酸二無
水物又は−無水物などが挙げられる。 As a polycarboxylic acid having an acid anhydride group,
For example, trimellitic anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, 3,4,
Tricarboxylic acid anhydrides such as 4'-benzophenone tricarboxylic acid-3, 4'-anhydride, 1, 2, 3, 4
-butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, ethylenetetracarboxylic acid, bicyclo-[2.2.2]-oct-(7)-ene-2:
3・5: Aliphatic and alicyclic tetrabasic acids such as 6-tetracarboxylic acid, pyromellitic acid, 3・3′・
4,4'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether,
2,3,6,7-naphthalenetetracarboxylic acid,
1, 2, 5, 6-naphthalenetetracarboxylic acid,
Ethylene glycol bistrimelitate, 2.
2'-bis(3,4-biscarboxyphenyl)propane, 2,2',3,3'-, or 3,3',4,
4'-Bisphenyltetracarboxylic acid, perylene-
3,4,9,10-tetracarboxylic acid, bis3,4
-Dicarboxyphenyl sulfone, 2,2-bis[4-(2,3- or 3,4-dicarboxyphenoxy)phenyl]propane, 4-(2,3-dicarboxyphenoxy)- Aromatic tetrabasic acids such as 4'-(3,4-dicarboxyphenoxy)-diphenyl-2,2-propane, thiophene-2,3,
Examples include tetrabasic acid dianhydrides or -anhydrides such as heterocyclic tetrabasic acids such as 4,5-tetracarboxylic acid and pyrazinetetracarboxylic acid.
トリカルボン酸無水物などのフリーのカルボキ
シル基をもつ酸無水物基を含有するポリカルボン
酸とポリイソシアネートとからポリアミドイミド
が得られる。また、テトラカルボン酸二無水物な
どの酸無水物基のみをもつ酸無水物基を有するポ
リカルボン酸とポリイソシアネートとからポリイ
ミドが得られる。一般的には耐熱性、コスト面等
を考慮すればトリメリツト酸無水物、２・２−ビ
ス〔４−（３・４−ジカルボキシフエノキシ）フ
エニル〕プロパン二無水物、３・3′・４・4′ベン
ゾフエノンテトラカルボン酸二無水物又はピロメ
リツト酸二無水物が好ましい。 A polyamideimide is obtained from a polycarboxylic acid containing an acid anhydride group having a free carboxyl group, such as tricarboxylic anhydride, and a polyisocyanate. Further, a polyimide can be obtained from a polycarboxylic acid having only an acid anhydride group, such as tetracarboxylic dianhydride, and a polyisocyanate. Generally speaking, considering heat resistance, cost, etc., trimellitic anhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 3,3', 4,4'benzophenonetetracarboxylic dianhydride or pyromellitic dianhydride is preferred.
ポリカルボン酸としては、例えばトリメリツト
酸、トリメシン酸、トリス（２−カルボキシエチ
ル）イソシアヌレート、テレフタル酸、イソフタ
ル酸、コハク酸、アジピン酸、２・５−、２・６
−又は３・６−ジカルボキシトルエン、２・６−
ジカルボキシナフタレン、３・3′−又は４・4′−
ジカルボキシビフエニル、ビス（３−又は４−カ
ルボキシフエニル）エーテル、ビス（３−又は４
−カルボキシフエニル）ケトン、ビス（３又は４
−カルボキシフエニル）スルホン、ビス（３−又
は４−カルボキフエニル）メタン、ビス（３−又
は４−カルボキシフエニル）ジメチルメタン、ピ
ロメリツト酸、トリカルバリリツク酸、ニトリロ
三酢酸、ニトリロ三プロピオン酸、アジピン酸、
セバシン酸又はドデカンジカルボン酸などが用い
られる。耐熱性などを考慮すれば、イソフタル
酸、テレフタル酸、トリメシン酸、トリス（２−
カルボキシエチル）イソシアヌレート又はニトリ
ロ三酢酸が好ましい。ポリイソシアネートと酸無
水物基を有するポリカルボン酸及び／又はポリカ
ルボン酸の使用量は、ポリイソシアネートの全イ
ソシアネート基に対して酸無水物基を有するポリ
カルボン酸及び／又はポリカルボン酸の全カルボ
キシル基の当量比（全カルボキシル基／全イソシ
アネート基）が1.0〜2.0の範囲内とすることが好
ましい。ここで、酸無水物基１当量はカルボキシ
ル基１当量として取り扱う。十分に高分子量であ
つて高度な耐熱性、可とう性を有する粒子状重合
体が要求される場合には、イソシアネート基に対
するカルボキシル基の当量比が好ましくは1.0〜
1.15、より好ましくは実質的に当量となるように
調整される。 Examples of polycarboxylic acids include trimellitic acid, trimesic acid, tris(2-carboxyethyl)isocyanurate, terephthalic acid, isophthalic acid, succinic acid, adipic acid, 2.5-, 2.6
- or 3,6-dicarboxytoluene, 2,6-
Dicarboxynaphthalene, 3/3'- or 4/4'-
dicarboxybiphenyl, bis(3- or 4-carboxyphenyl) ether, bis(3- or 4-carboxyphenyl)
-carboxyphenyl)ketone, bis(3 or 4
-carboxyphenyl) sulfone, bis(3- or 4-carboxyphenyl)methane, bis(3- or 4-carboxyphenyl)dimethylmethane, pyromellitic acid, tricarbalyllic acid, nitrilotriacetic acid, nitrilotripropionic acid, adipine acid,
Sebacic acid or dodecanedicarboxylic acid is used. Considering heat resistance, isophthalic acid, terephthalic acid, trimesic acid, tris(2-
Preferred are carboxyethyl) isocyanurate or nitrilotriacetic acid. The amount of polyisocyanate and polycarboxylic acid and/or polycarboxylic acid having an acid anhydride group to be used is based on the total amount of polycarboxylic acid and/or polycarboxylic acid having an acid anhydride group relative to the total isocyanate group of the polyisocyanate. The equivalent ratio of groups (total carboxyl groups/total isocyanate groups) is preferably within the range of 1.0 to 2.0. Here, 1 equivalent of acid anhydride group is treated as 1 equivalent of carboxyl group. When a particulate polymer having a sufficiently high molecular weight and high heat resistance and flexibility is required, the equivalent ratio of carboxyl groups to isocyanate groups is preferably 1.0 to 1.0.
1.15, more preferably substantially equivalent.
連続相となる非水有機液体と分散相となる反応
剤との量比は非水有機液体と反応剤との総量に対
して反応剤が10〜80重量％となる範囲が好まし
い。生産効率、コスト上の観点から40重量％以上
が特に好ましい。 The ratio of the amount of the non-aqueous organic liquid as the continuous phase to the reactant as the dispersed phase is preferably within a range of 10 to 80% by weight of the reactant based on the total amount of the non-aqueous organic liquid and the reactant. From the viewpoint of production efficiency and cost, it is particularly preferably 40% by weight or more.
分散安定剤と反応剤との量比は分散安定剤と反
応剤との総量に対して分散安定剤が0.5重量％以
上が好ましい。耐熱性やコスト面等を考慮すると
２〜20％となる範囲がとくに好ましい。 The amount ratio of the dispersion stabilizer to the reactant is preferably 0.5% by weight or more based on the total amount of the dispersion stabilizer and the reactant. Considering heat resistance, cost, etc., a range of 2 to 20% is particularly preferable.
分散安定剤は通常溶液の形で製造され、溶液の
形で使用されるが、その使用量は例えば170℃で
２時間乾燥後の溶液中の不揮発分の重量により計
算される。 The dispersion stabilizer is usually produced and used in the form of a solution, and the amount used is calculated, for example, by the weight of nonvolatile matter in the solution after drying at 170° C. for 2 hours.
また、本発明はゲル化した粒子状重合体も得る
ことができる。ゲル化した粒子状重合体を得るに
はゲル化するに充分な３官能以上の架橋成分を含
む樹脂組成で反応をゲル化するまで進めれば良
い。前記したポリイソシアネートのうち３官能以
上の架橋成分となりうるものとしては、ジイソシ
アネートを三量化して得られる化合物、例えばト
リレンジイソシアネート、キシリレンジイソシア
ネート、４・4′−ジフエニルエーテルジイソシア
ネート、ナフタレン−１・５−ジイソシアネー
ト、４・4′−ジフエニルメタンジイソシアネート
等の芳香族ジイソシアネートの三量体、エチレン
ジイソシアネート、１・４−テトラメチレンジイ
ソシアネート、１・６−ヘキサメチレンジイソシ
アネート、１・12−ドデカンジイソシアネート等
の芳香族ジイソシアネートの三量体、シクロブテ
ン−１・３−ジイソシアネート、シクロヘキサン
−１・３−および１・４−ジイソシアネート、イ
ソフオロンジイソシアネート等の脂環式ジイソシ
アネートの三量体、トリイソシアネート化合物、
例えばトリフエニルメタン−４・4′・4″−トリイ
ソシアネート、ポリフエニルメチルポリイソシア
ネート、例えばアニリンとフオルムアルデヒドと
の縮合物とホスゲンを反応させたものなどが用い
られる。これらの架橋成分となりうるポリイソシ
アネートは、ポリイソシアネート成分の全部又は
一部に用いることができる。 Moreover, the present invention can also obtain a gelled particulate polymer. In order to obtain a gelled particulate polymer, the reaction may be allowed to proceed until gelation is achieved using a resin composition containing a trifunctional or higher functional crosslinking component sufficient for gelation. Among the polyisocyanates described above, those that can be trifunctional or higher-functional crosslinking components include compounds obtained by trimerizing diisocyanates, such as tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, and naphthalene-1.・Trimers of aromatic diisocyanates such as 5-diisocyanate and 4,4'-diphenylmethane diisocyanate, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, etc. trimers of aromatic diisocyanates, cyclobutene-1,3-diisocyanate, cyclohexane-1,3- and 1,4-diisocyanates, trimers of alicyclic diisocyanates such as isophorone diisocyanate, triisocyanate compounds,
For example, triphenylmethane-4,4',4''-triisocyanate, polyphenylmethyl polyisocyanate, for example, a product obtained by reacting a condensate of aniline and formaldehyde with phosgene, etc. are used. These can be used as crosslinking components. Polyisocyanate can be used for all or part of the polyisocyanate component.
前記した酸無水物基を有するポリカルボン酸及
び／又はポリカルボン酸のうち３官能以上の架橋
成分となり得るものとしてはトリメリツト酸、ト
リメシン酸、ピロメリツト酸、トリス（２−カル
ボキエチル）イソシアヌレートトリカルバリリツ
ク酸、ニトロ三酢酸、ニトリロ三プロピオン酸な
どが用いられる。本発明においてはポリイソシア
ネートと反応される酸無水物基を有するポリカル
ボン酸及びポリカルボン酸は両者か又はいずれか
が用いられる。これらの架橋成分となりうるポリ
カルボン酸は、酸無水物基を有するポリカルボン
酸及び／又はポリカルボン酸の全部又は一部に用
いることができる。 Among the polycarboxylic acids and/or polycarboxylic acids having an acid anhydride group, those which can serve as trifunctional or higher functional crosslinking components include trimellitic acid, trimesic acid, pyromellitic acid, and tris(2-carboxyethyl)isocyanurate tricarboxylic acid. Litric acid, nitrotriacetic acid, nitrilotripropionic acid, etc. are used. In the present invention, either or both of the polycarboxylic acid and the polycarboxylic acid having an acid anhydride group which are reacted with the polyisocyanate are used. These polycarboxylic acids that can serve as crosslinking components can be used for all or part of the polycarboxylic acid and/or polycarboxylic acid having an acid anhydride group.
以上述べた３官能以上の架橋成分を用いてゲル
化した粒子状重合体を得る方法の他に副反応を利
用してゲル化させる方法などもある。例えば、２
官能同士のポリイソシアネートと酸無水物基を有
するポリカルボン酸及び／又はポリカルボン酸の
当量比を実質1.0で反応させる際に120℃以上の高
温で、反応を長時間進めると副反応によりゲル化
した粒子状重合体が得られる。 In addition to the above-mentioned method of obtaining a gelled particulate polymer using a trifunctional or higher functional crosslinking component, there is also a method of gelling using a side reaction. For example, 2
When reacting functional polyisocyanate and polycarboxylic acid and/or polycarboxylic acid having an acid anhydride group at an equivalent ratio of substantially 1.0, if the reaction is allowed to proceed for a long time at a high temperature of 120°C or higher, gelation occurs due to side reactions. A particulate polymer is obtained.
ポリイソシアネート、酸無水物基を有するポリ
カルボン酸及び／又はポリカルボン酸の反応温度
としては80〜350℃が好ましい。 The reaction temperature of polyisocyanate, polycarboxylic acid having an acid anhydride group and/or polycarboxylic acid is preferably 80 to 350°C.
重合反応は、実質上無水の状態で実施されるこ
とが好ましい。従つて、窒素ガスなどの不活性雰
囲気下で行なうのが望ましい。当然のことなが
ら、本発明の製造法によつて得られる粒子状重合
体はその反応剤、特にポリイソシアネートが水と
接触することによつて、すみやかに不活性な化合
物に変質するために、水を分散媒体として製造す
ることは不可能である。反応は、全ての原料を同
時に仕込んでもよいし、目的に応じて段階的に仕
込み、反応を進めてもよい。 Preferably, the polymerization reaction is carried out in substantially anhydrous conditions. Therefore, it is desirable to carry out the process under an inert atmosphere such as nitrogen gas. Naturally, when the particulate polymer obtained by the production method of the present invention comes into contact with water, its reactant, particularly polyisocyanate, quickly transforms into an inert compound. is not possible to produce as a dispersion medium. The reaction may be carried out by charging all the raw materials at the same time, or by charging them in stages depending on the purpose.
例えば段階的に仕込む方法としては、酸成分を
除く全成分を非水有機液体中に油滴状態で分散し
た不均一溶液に、微粉末化した酸成分を添加して
反応が進められる。又はポリイソシアネートを除
く全成分を非水有機液体中に油滴状態で分散した
不均一溶液にポリイソシアネートを添加して反応
を進めてもよい。重合反応中における粒子状重合
体の分散安定性を保持し、小粒化するために分散
安定剤を段階的に仕込む方法を用いてもよい。 For example, in a stepwise charging method, the reaction proceeds by adding a finely powdered acid component to a heterogeneous solution in which all components except the acid component are dispersed in the form of oil droplets in a non-aqueous organic liquid. Alternatively, the reaction may proceed by adding the polyisocyanate to a heterogeneous solution in which all components except the polyisocyanate are dispersed in the form of oil droplets in a non-aqueous organic liquid. In order to maintain the dispersion stability of the particulate polymer during the polymerization reaction and to reduce the particle size, a method may be used in which a dispersion stabilizer is introduced in stages.
本発明において得られる粒子状重合体は反応中
又は反応後に必要に応じてメタノール、ｎ−ブタ
ノール、ベンジルアルコール、ε−カプロラクタ
ム、メチルエチルケトンオキシム、アセトアルド
キシム、フエノール、クレゾールなどの活性水素
を分子内に１個有する適当なブロツク剤を添加反
応させて安定化させることができる。 The particulate polymer obtained in the present invention incorporates active hydrogen such as methanol, n-butanol, benzyl alcohol, ε-caprolactam, methyl ethyl ketone oxime, acetaldoxime, phenol, and cresol into the molecule as necessary during or after the reaction. Stabilization can be achieved by adding one suitable blocking agent.
反応におけるかくはん方法としては乳化器（ホ
モミキサー）による高速剪断を伴うかくはん方
法、プロペラ型かくはん器による粒子の機械的切
断、粉砕を伴わないかくはん方法などが用いられ
る。乳化器は重合体への反応剤の転換率が余り高
くない領域で使用することが好ましい。望ましい
かくはん方法としては、反応の初期に乳化器によ
つて粒子の小径化を行ない、その粒子の分散安定
性が良好なる粒子率付近でプロペラ型かくはん器
に代えて、さらに反応を進める方法がある。この
方法によれば、比較的小粒径で粒度のそろつた粒
子状重合体を得ることができる。合成系によつて
は反応前に乳化器を使用して微小粒子化すること
も可能である。 Stirring methods used in the reaction include stirring methods involving high-speed shearing using an emulsifier (homomixer), mechanical cutting of particles using a propeller-type stirrer, and stirring methods that do not involve pulverization. The emulsifier is preferably used in areas where the conversion of reactants to polymer is not very high. A desirable stirring method is to use an emulsifier to reduce the particle diameter at the beginning of the reaction, and then use a propeller-type stirrer to further advance the reaction at a particle rate near where the dispersion stability of the particles is good. . According to this method, a particulate polymer having a relatively small particle size and uniform particle size can be obtained. Depending on the synthesis system, it is also possible to use an emulsifier to form fine particles before the reaction.
本発明になる製造方法によれば、粒子状重合体
は非水有機液体中に分散されて得られ、分散相に
はこの粒子状重合体の他に分散安定剤、反応剤等
が含まれるが、これらは精製を行なうことによつ
て除去される。 According to the production method of the present invention, a particulate polymer is obtained by being dispersed in a nonaqueous organic liquid, and the dispersed phase contains a dispersion stabilizer, a reactant, etc. in addition to this particulate polymer. , these are removed by performing purification.
本法において得られる粒子状重合体は、平均粒
度が0.05〜2000μｍ及びそれ以上の範囲にある非
塊状の粒子形態で得られる。好ましい平均粒度は
0.1〜500μｍ、最も好ましいものは0.5〜100μｍ
である。かかる粒子状重合体の回収方法は過又
はデカンテーシヨンし、次いで常圧又は減圧下で
乾燥することによつて分散体溶液から回収でき
る。 The particulate polymer obtained in this method is obtained in the form of non-agglomerated particles with an average particle size ranging from 0.05 to 2000 μm and above. The preferred average particle size is
0.1-500μm, most preferably 0.5-100μm
It is. The particulate polymer can be recovered from the dispersion solution by filtration or decantation and then drying under normal pressure or reduced pressure.
本発明によつて得られる粒子状重合体に必要に
応じて、フツ素樹脂、エポキシ樹脂、アミノ樹
脂、フエノールホルムアルデヒド樹脂、イソシア
ヌレート環含有ポリイソシアネート及び酸成分と
してテレフタル酸及び／又はイソフタル酸を用い
て得られる水酸基を有するポリエステル樹脂のい
ずれか１又は２以上を添加して、複合材料とする
ことができる。エポキシ樹脂としてはエピコート
828、1001、1004、1007等のビスフエノール系エ
ポキシ樹脂、DEN431、438（以上、ダウ・ケミ
カル社製商品名）等のエポキシ化ノボラツク樹
脂、トリグリシジルイソシアヌレートなどが好ま
しい。アミノ樹脂としてはメラミンホルムアルデ
ヒド樹脂及びこのアルコキシ変性樹脂、例えばブ
トキシベンゾグアナミンホルムアルデヒド樹脂、
ヘキサメトキシメラミン樹脂などが好ましい。フ
エノールホルムアルデヒド樹脂としては、フエノ
ールホルムアルデヒド樹脂、アルキルフエノール
ホルムアルデヒド樹脂、これらの樹脂を主体とし
たメラミン変性フエノールホルムアルデヒド樹
脂、ベンゾグアナミン変性フエノールホルムアル
デヒド樹脂などが好ましい。イソシアヌレート環
含有ポリイソシアネートとしては芳香族ジイソシ
アネート、特にトリレンジイソシアネートを第三
級アミンの存在下で反応させて得られる三量体又
は三量体を含むイソシアヌレート環含有ポリイソ
シアネート混合物等が好ましい。酸成分としてテ
レフタル酸及び／又はイソフタル酸を用いて得ら
れる水酸基を有するポリエステル樹脂としては、
分岐成分としてトリス（２−ヒドロキシエチル）
イソシアヌレートを用いたポリエステル樹脂、ポ
リエステルイミド樹脂、ポリエステルアミド樹脂
などが好ましい。このような粒子状重合体及びそ
の複合材料は良好な耐熱性、機械特性、電気特性
を示し、耐熱塗料、耐熱シート、耐熱接着剤、耐
熱積層材料、耐熱摺動材料、耐熱成形モールド
品、ガラス繊維、炭素繊維との耐熱複合材料など
に有用である。 If necessary, a fluororesin, an epoxy resin, an amino resin, a phenol formaldehyde resin, an isocyanurate ring-containing polyisocyanate, and terephthalic acid and/or isophthalic acid are used as an acid component in the particulate polymer obtained by the present invention. A composite material can be prepared by adding one or more of the polyester resins having hydroxyl groups obtained by the following methods. Epicote is an epoxy resin.
Preferred are bisphenol epoxy resins such as 828, 1001, 1004, and 1007, epoxidized novolac resins such as DEN431 and 438 (trade names manufactured by Dow Chemical Company), and triglycidyl isocyanurate. As amino resins, melamine formaldehyde resins and alkoxy-modified resins thereof, such as butoxybenzoguanamine formaldehyde resins,
Hexamethoxymelamine resin and the like are preferred. Preferred examples of the phenol formaldehyde resin include phenol formaldehyde resins, alkyl phenol formaldehyde resins, melamine-modified phenol formaldehyde resins based on these resins, and benzoguanamine-modified phenol formaldehyde resins. The isocyanurate ring-containing polyisocyanate is preferably a trimer obtained by reacting an aromatic diisocyanate, particularly tolylene diisocyanate in the presence of a tertiary amine, or a mixture of isocyanurate ring-containing polyisocyanates containing the trimer. As a polyester resin having a hydroxyl group obtained using terephthalic acid and/or isophthalic acid as an acid component,
Tris(2-hydroxyethyl) as a branching component
Preferred are polyester resins, polyesterimide resins, polyesteramide resins, etc. using isocyanurate. Such particulate polymers and their composite materials exhibit good heat resistance, mechanical properties, and electrical properties, and are useful in heat-resistant paints, heat-resistant sheets, heat-resistant adhesives, heat-resistant laminated materials, heat-resistant sliding materials, heat-resistant molded products, and glass. It is useful for heat-resistant composite materials with fibers and carbon fibers.
特に微粒子系では比較的安定な分散系が得られ
るので、分散体溶液のままで分散塗料として利用
することもできる。 In particular, since a relatively stable dispersion system can be obtained in the case of a fine particle system, the dispersion solution can also be used as a dispersion paint.
更にゲル化した粒子状重合体は、耐熱揺変剤、
耐熱充填剤、潤滑油の増稠剤、無機元素の吸着
剤、有機化合物の分離材料などに有用である。 Furthermore, the gelled particulate polymer is treated with a heat thixotropic agent,
It is useful as a heat-resistant filler, a lubricating oil thickener, an adsorbent for inorganic elements, and a separation material for organic compounds.
本発明を実施例を用いて説明する。 The present invention will be explained using examples.
実施例 １
(1) 分散安定剤の合成
温度計、かきまぜ機、球管冷却器を付けた四
つ口フラスコに、ISOPAR−Ｈ（エツソスタン
ダード石油社製脂肪族炭化水素、商品名）152
ｇ、ラウリルメタクリレート74.5ｇ、メタクリ
ル酸−２−ヒドロキシエチル10.2ｇを入れ、
120℃に昇温した。窒素ガスを通しながら、あ
らかじめ調製したラウリルメタクリレート74.5
ｇ、メタクリル酸−２−ヒドロキシエチル40.8
ｇ、過酸化ベンゾイルベースト（過酸化ベンゾ
イルの含分50重量％）２ｇの混合物をかくはん
しながら２時間かけて滴下した。引き続き120
℃でISOPAR−H100ｇを１時間かけて滴下
し、140℃に昇温し、同温度で４時間反応させ
た。この分散安定剤溶液は170℃で２時間乾燥
した時の不揮発分が51重量％であり、分散安定
剤の数平均分子量（分子量既知のポリスチレン
を検量線とするゲルパーミエーシヨンクロマト
グラフイ法によつて求めた。以下同じ）は
45000であつた。Example 1 (1) Synthesis of dispersion stabilizer ISOPAR-H (aliphatic hydrocarbon manufactured by Etsuo Standard Oil Co., Ltd., trade name) 152 was placed in a four-necked flask equipped with a thermometer, a stirrer, and a bulb condenser.
g, 74.5 g of lauryl methacrylate, and 10.2 g of 2-hydroxyethyl methacrylate.
The temperature was raised to 120℃. Pre-prepared lauryl methacrylate 74.5 while passing nitrogen gas
g, 2-hydroxyethyl methacrylate 40.8
A mixture of 2 g of benzoyl peroxide base (benzoyl peroxide content: 50% by weight) was added dropwise over 2 hours with stirring. Continued to 120
100 g of ISOPAR-H was added dropwise over 1 hour at ℃, the temperature was raised to 140 ℃, and the mixture was reacted at the same temperature for 4 hours. This dispersion stabilizer solution had a nonvolatile content of 51% by weight when dried at 170°C for 2 hours, and the number average molecular weight of the dispersion stabilizer (gel permeation chromatography method using polystyrene of known molecular weight as a calibration curve) (The same applies hereafter) is
It was 45,000.
(2) 粒子状重合体の合成
温度計、かきまぜ機、球管冷却器を付けた四
ツ口フラスコに窒素ガスを通しながら、４・
4′−ジフエニルメタンジイソシアネート75ｇ、
(1)で得た分散安定剤溶液19ｇ、ISOPAR−
H150ｇを入れ、かくはんしながら90℃に昇温
した。この状態でこれらの混合物は均一溶液と
なつた。あらかじめ、微粉末化したトリメリツ
ト酸無水物72ｇを添加し、100℃で１時間、140
℃で１時間、さらに180℃に昇温して４時間反
応を進めた。連続相のISOPAR−Ｈ中に分散し
た褐色の粒子状重合体を得たので、これを過
によつて回収し、ｎ−ヘキサン及びメタノール
で精製したのち、減圧下、60℃で５時間乾燥さ
せた。この粒子状重合体の赤外吸収スペクトル
には、1780cm-1にイミド結合、1650cm-1と1540
cm-1にアミド結合の吸収が認められた。このポ
リアミドイミド粒子状重合体の主粒子径は約10
〜30μｍであつた。(2) Synthesis of particulate polymer While passing nitrogen gas through a four-necked flask equipped with a thermometer, stirrer, and bulb condenser, 4.
75g of 4'-diphenylmethane diisocyanate,
19g of the dispersion stabilizer solution obtained in (1), ISOPAR-
150g of H was added and the temperature was raised to 90°C while stirring. In this state, these mixtures became a homogeneous solution. 72 g of finely powdered trimellitic anhydride was added in advance, and the mixture was heated at 100°C for 1 hour at 140°C.
The reaction was continued at 180°C for 1 hour and then raised to 180°C for 4 hours. A brown particulate polymer dispersed in the continuous phase ISOPAR-H was obtained, which was recovered by filtration, purified with n-hexane and methanol, and then dried at 60°C for 5 hours under reduced pressure. Ta. The infrared absorption spectrum of this particulate polymer includes an imide bond at 1780 cm -1 and an imide bond at 1650 cm -1 and 1540 cm -1.
Absorption of amide bond was observed at cm -1 . The main particle diameter of this polyamide-imide particulate polymer is approximately 10
It was ~30 μm.
実施例 ２
実施例１、(2)と動同じ装置を用いて、窒素ガス
を通しながらトリメリツト酸無水物基59.3ｇ、実
施例１、(1)で得た分散安定剤溶液26ｇ、流動パラ
フイン150ｇを入れ、強力にかくはんしながら180
℃に昇温した。この状態で混合物は連続相と分散
相を形成しエマルジヨン化した。これに液状の
４・4′−ジフエニルメタンジイソシアネート75ｇ
を２時間で滴下した。引き続き同温度で６時間反
応させた。流動パラフイン中に分散した褐色の粒
子状重合体を得たので、これを過によつて回収
し、ｎ−ヘキサン、メタノールで洗浄したのち、
減圧下、60℃で５時間乾燥させた。この粒子状重
合体の赤外吸収スペクトルには、1780cm-1にイミ
ド結合、1650cm-1と1540cm-1にアミド結合の吸収
が認められた。この粒子状重合体の主粒子径は約
10〜60μｍであつた。Example 2 Using the same apparatus as in Example 1, (2), while passing nitrogen gas, 59.3 g of trimellitic acid anhydride group, 26 g of the dispersion stabilizer solution obtained in Example 1, (1), and 150 g of liquid paraffin were added. 180% while stirring vigorously.
The temperature was raised to ℃. In this state, the mixture formed a continuous phase and a dispersed phase to form an emulsion. Add to this 75g of liquid 4,4'-diphenylmethane diisocyanate.
was added dropwise over 2 hours. Subsequently, the reaction was continued at the same temperature for 6 hours. A brown particulate polymer dispersed in liquid paraffin was obtained, which was collected by filtration and washed with n-hexane and methanol.
It was dried at 60° C. for 5 hours under reduced pressure. In the infrared absorption spectrum of this particulate polymer, imide bond absorption was observed at 1780 cm -1 and amide bond absorption was observed at 1650 cm -1 and 1540 cm -1 . The main particle diameter of this particulate polymer is approximately
It was 10 to 60 μm.
実施例 ３
(1) 分散安定剤の合成
実施例１、(1)と同様の装置を用いて、フラス
コにISOPAR−H92.9ｇ、ラウリルメタクリレ
ート106.8ｇ、メタクリル酸−２−ヒドロキシ
エチル6.1ｇを入れ、80℃に昇温した。窒素ガ
スを通しながら、あらかじめ調整したラウリル
メタクリレート106.9ｇ、メタクリル酸−２−
ヒドロキシエチル24.5ｇ、過酸化ベンゾイルペ
ースト1.2ｇの混合物をかくはんしながら２時
間かけて滴下した。引き続き80℃でISOPAR−
H92.8ｇを１時間かけて滴下し、更に80℃で１
時間保温後、140℃に昇温し、同温度で４時間
反応させた。この分散安定剤溶液は170℃で２
時間乾燥した時の不揮発分は47重量％であり、
分散安定剤の数平均分子量は290000であつた。Example 3 (1) Synthesis of dispersion stabilizer Using the same equipment as in Example 1 (1), 92.9 g of ISOPAR-H, 106.8 g of lauryl methacrylate, and 6.1 g of 2-hydroxyethyl methacrylate were placed in a flask. , the temperature was raised to 80℃. While passing nitrogen gas, 106.9 g of lauryl methacrylate, methacrylic acid-2- prepared in advance.
A mixture of 24.5 g of hydroxyethyl and 1.2 g of benzoyl peroxide paste was added dropwise over 2 hours with stirring. Continue to ISOPAR− at 80℃
92.8g of H was added dropwise over 1 hour, and then heated to 80°C for 1 hour.
After keeping the temperature for an hour, the temperature was raised to 140°C, and the reaction was continued at the same temperature for 4 hours. This dispersion stabilizer solution was
The non-volatile content when dried for hours is 47% by weight,
The number average molecular weight of the dispersion stabilizer was 290,000.
(2) 粒子状重合体の合成
実施例１、(2)と同じ装置を用いて、窒素ガス
を通しながら、４・4′−ジフエニルメタンジイ
ソシアネート75ｇ、ピロメリツト酸二無水物
81.8ｇ、(1)で得た分散安定剤溶液25ｇ、
ISOPAR−H150ｇを入れ、かくはんしながら
100℃に昇温した。100℃で１時間、140℃で１
時間、されに180℃に昇温して４時間反応を進
めた。ISOPAR−Ｈ中に分散した褐色の粒子状
重合体を得たので、これを過によつて回収
し、ｎ−ヘキサン、メタノールで精製したの
ち、減圧下、60℃で５時間乾燥させた。この粒
子状重合体の赤外吸収スペクトルには1780cm-1
にイミド結合の吸収は認められたが、1650cm-1
と1540cm-1のアミド結合の吸収は認められなか
つた。このポリイミド粒子状重合体の主粒子径
は約５〜50μｍであつた。(2) Synthesis of particulate polymer Using the same equipment as in Example 1 and (2), 75 g of 4,4'-diphenylmethane diisocyanate and pyromellitic dianhydride were added while passing nitrogen gas.
81.8g, 25g of the dispersion stabilizer solution obtained in (1),
Add 150g of ISOPAR-H and stir while stirring.
The temperature was raised to 100℃. 1 hour at 100℃, 1 hour at 140℃
Afterwards, the temperature was raised to 180°C and the reaction proceeded for 4 hours. A brown particulate polymer dispersed in ISOPAR-H was obtained, which was recovered by filtration, purified with n-hexane and methanol, and then dried at 60° C. for 5 hours under reduced pressure. The infrared absorption spectrum of this particulate polymer is 1780 cm -1
Absorption of imide bonds was observed at 1650 cm -1
No absorption of the amide bond at 1540 cm -1 was observed. The main particle diameter of this polyimide particulate polymer was about 5 to 50 μm.
実施例 ４
(1) 分散安定剤の合成
実施例１、(1)と同様の装置を用いて、フラス
コにISOPAR−H100ｇ、ステアリルメタクリ
レート142.2ｇ、メタクリル酸−２−ヒドロキ
シエチル12.2ｇを入れ、100℃に昇温した。窒
素ガスを通しながら、あらかじめ調整した、
ISOPAR−H85.7ｇ、ステアリルメタクリレー
ト142.2ｇ、メタクリル酸−２−ヒドロキシエ
チル49.0ｇ、過酸化ベンゾイルペースト4.8ｇ
の混合物をかくはんしながら２時間かけて滴下
した。引き続き100℃で１時間保温した後140℃
に昇温し、同温度で４時間反応させた。この分
散安定剤溶液は170℃で２時間乾燥した時の不
揮発分は51重量％であり、分散安定剤の数平均
分子量は65000であつた。Example 4 (1) Synthesis of dispersion stabilizer Using the same equipment as in Example 1 (1), put 100 g of ISOPAR-H, 142.2 g of stearyl methacrylate, and 12.2 g of 2-hydroxyethyl methacrylate into a flask, and add 100 g of 2-hydroxyethyl methacrylate. The temperature was raised to ℃. Pre-adjusted while passing nitrogen gas,
ISOPAR-H 85.7g, stearyl methacrylate 142.2g, 2-hydroxyethyl methacrylate 49.0g, benzoyl peroxide paste 4.8g
The mixture was added dropwise over 2 hours while stirring. Continue to keep warm at 100℃ for 1 hour and then heat to 140℃
The temperature was raised to 1, and the reaction was continued at the same temperature for 4 hours. When this dispersion stabilizer solution was dried at 170° C. for 2 hours, the nonvolatile content was 51% by weight, and the number average molecular weight of the dispersion stabilizer was 65,000.
(2) 粒子状重合体の合成
実施例１、(2)と同じ装置を用いて、窒素ガス
を通しながら、４・4′−ジフエニルエーテルジ
イソシアネート74.4ｇ、(1)で得た分散安定剤溶
液19ｇ、ISOPAR−H150ｇを入れ、かくはん
しながら90℃に昇温した。あらかじめ微粉末化
したトリメリツト酸無水物63.4ｇを添加し、
100℃で１時間、140℃で１時間、されに180℃
に昇温して５時間反応を進めた。ISOPAR−Ｈ
中に分散した黄色の粒子状重合体を得たので、
これを過によつて回収し、ｎ−ヘキサン、メ
タノールで精製したのち、減圧下、60℃で５時
間乾燥させた。この粒子状重合体の赤外吸収ス
ペクトルには1780cm-1にイミド結合、1650cm-1
と1540cm-1にアミド結合の吸収が認められた。
このポリイミド粒子状重合体の主粒子径は約10
〜30μｍであつた。(2) Synthesis of particulate polymer Using the same equipment as in Example 1 and (2), while passing nitrogen gas, 74.4 g of 4,4'-diphenyl ether diisocyanate and the dispersion stabilizer obtained in (1) were added. 19 g of the solution and 150 g of ISOPAR-H were added, and the temperature was raised to 90°C while stirring. Add 63.4 g of trimellitic anhydride that has been finely powdered in advance,
1 hour at 100℃, 1 hour at 140℃, then 180℃
The reaction was allowed to proceed for 5 hours. ISOPAR-H
Now that we have obtained a yellow particulate polymer dispersed in
This was collected by filtration, purified with n-hexane and methanol, and then dried at 60° C. for 5 hours under reduced pressure. The infrared absorption spectrum of this particulate polymer includes an imide bond at 1780 cm -1 and an imide bond at 1650 cm -1.
An amide bond absorption was observed at 1540 cm -1 .
The main particle diameter of this polyimide particulate polymer is approximately 10
It was ~30 μm.
実施例 ５
(1) 分散安定剤の合成
実施例１、(1)と同様の装置を用いて、フラス
コにISOPAR−H100ｇ、ステアリルメタクリ
レート142.2ｇ、メタクリル酸グリシジル13.3
ｇを入れ、100℃に昇温した。窒素ガスを通し
ながら、あらかじめ調整したISOPAR−H85.7
ｇ、ステアリルメタクリレート142.2ｇ、メタ
クリル酸グリシジル53.5ｇ、過酸化ベンゾイル
ペースト4.8ｇの混合物をかくはんしながら２
時間かけて滴下した。引き続き100℃で１時間
保温した後140℃に昇温し、同温度で４時間反
応させた。この分散安定剤溶液は170℃で２時
間乾燥した時の不揮発分は55重量％であり、分
散安定剤の数平均分子量は18000であつた。Example 5 (1) Synthesis of dispersion stabilizer Using the same equipment as in Example 1 (1), 100 g of ISOPAR-H, 142.2 g of stearyl methacrylate, and 13.3 g of glycidyl methacrylate were placed in a flask.
g and the temperature was raised to 100°C. ISOPAR-H85.7 adjusted in advance while passing nitrogen gas
2 while stirring a mixture of 142.2 g of stearyl methacrylate, 53.5 g of glycidyl methacrylate, and 4.8 g of benzoyl peroxide paste.
It dripped over time. Subsequently, the mixture was kept at 100°C for 1 hour, then raised to 140°C, and reacted at the same temperature for 4 hours. When this dispersion stabilizer solution was dried at 170°C for 2 hours, the nonvolatile content was 55% by weight, and the number average molecular weight of the dispersion stabilizer was 18,000.
(2) 粒子状重合体の合成
実施例１、(2)と同じ装置を用いて、窒素ガス
を通しながら、４・4′−ジフエニルメタンジイ
ソシアネート75ｇ、(1)で得た分散安定剤溶液
（不揮発分55重量％）19ｇ、ISOPAR−H150ｇ
を入れ、かくはんしながら90℃に昇温した。あ
らかじめ微粉末化したトリメリツト酸無水物72
ｇを添加し、100℃で１時間、140℃で１時間、
されに180℃に昇温して４時間反応を進めた。
ISOPAR−Ｈ中に分散した黄色の粒子状重合体
を得たので、これを過によつて回収し、ｎ−
ヘキサン、メタノールで精製したのち、減圧
下、60℃で５時間乾燥させた。この粒子状重合
体の赤外吸収スペクトルには1780cm-1にイミド
結合、1650cm-1と1540cm-1にアミド結合の吸収
が認められた。このポリイミド粒子状重合体の
主粒子径は約20〜60μｍであつた。(2) Synthesis of particulate polymer Using the same equipment as in Example 1 and (2), while passing nitrogen gas, 75 g of 4,4'-diphenylmethane diisocyanate and the dispersion stabilizer solution obtained in (1) were added. (Non-volatile content 55% by weight) 19g, ISOPAR-H 150g
was added, and the temperature was raised to 90°C while stirring. Pre-micronized trimellitic anhydride 72
g, and heated at 100℃ for 1 hour, then at 140℃ for 1 hour,
Then, the temperature was raised to 180°C and the reaction proceeded for 4 hours.
A yellow particulate polymer dispersed in ISOPAR-H was obtained, which was recovered by filtration and n-
After purification with hexane and methanol, it was dried at 60°C for 5 hours under reduced pressure. In the infrared absorption spectrum of this particulate polymer, imide bond absorption was observed at 1780 cm -1 and amide bond absorption was observed at 1650 cm -1 and 1540 cm -1 . The main particle diameter of this polyimide particulate polymer was about 20 to 60 μm.
実施例 ６
(1) 分散安定剤の合成
実施例１、(1)と同様の装置を用いて、フラス
コにISOPAR−H152ｇ、ステアリルメタクリ
レート83ｇ、メタクリル酸グリシジル7.4ｇを
入れ、100℃に昇温した。窒素ガスを通しなが
ら、あらかじめ調整したラウリルメタクリレー
ト83ｇ、メタクリル酸グリシジル29.8ｇ、過酸
化ベンゾイルペースト20ｇの混合物をかくはん
しながら２時間かけて滴下した。引き続き140
℃に昇温し、同温度で５時間反応させた。この
分散安定剤溶液は170℃で２時間乾燥した時の
不揮発分は42.2重量％であり、分散安定剤の数
平均分子量は54000であつた。Example 6 (1) Synthesis of dispersion stabilizer Using the same equipment as in Example 1 (1), 152 g of ISOPAR-H, 83 g of stearyl methacrylate, and 7.4 g of glycidyl methacrylate were placed in a flask, and the temperature was raised to 100°C. . While passing nitrogen gas, a mixture of 83 g of lauryl methacrylate, 29.8 g of glycidyl methacrylate, and 20 g of benzoyl peroxide paste prepared in advance was added dropwise over 2 hours while stirring. Continuing to 140
The temperature was raised to .degree. C., and the reaction was continued at the same temperature for 5 hours. When this dispersion stabilizer solution was dried at 170°C for 2 hours, the nonvolatile content was 42.2% by weight, and the number average molecular weight of the dispersion stabilizer was 54,000.
(2) 粒子状重合体の合成
実施例１、(2)と同じ装置を用いて、窒素ガス
を通しながら、４・4′−ジフエニルメタンジイ
ソシアネート75ｇ、イソフタル酸62.2ｇ、本実
施例(1)で得た分散安定剤溶液（不揮発分42.2重
量％）19ｇ、ISOPAR−H150ｇを入れ、かく
はんしながら昇温し、100℃で１時間、140℃で
１時間、さらに180℃に昇温して４時間反応を
進めた。ISOPAR−Ｈ中に分散した白黄色の粒
子状重合体を得たので、これを過によつて回
収し、ｎ−ヘキサン、メタノールで精製したの
ち、減圧下、60℃で５時間乾燥させた。この粒
子状重合体の赤外吸収スペクトルには1780cm-1
のイミド結合は認められず、1650cm-1と1540cm
-1のアミド結合の吸収は認められた。このポリ
アミド粒子状重合体の主粒子径は約10〜80μｍ
であつた。(2) Synthesis of particulate polymer Using the same equipment as in Examples 1 and (2), while passing nitrogen gas, 75 g of 4,4'-diphenylmethane diisocyanate, 62.2 g of isophthalic acid, and this example (1) were added. ), 19 g of the dispersion stabilizer solution (non-volatile content: 42.2% by weight) and 150 g of ISOPAR-H were added, heated while stirring, heated to 100°C for 1 hour, 140°C for 1 hour, and further heated to 180°C. The reaction proceeded for 4 hours. A white-yellow particulate polymer dispersed in ISOPAR-H was obtained, which was recovered by filtration, purified with n-hexane and methanol, and then dried at 60°C under reduced pressure for 5 hours. The infrared absorption spectrum of this particulate polymer is 1780 cm -1
No imide bond was observed, 1650 cm -1 and 1540 cm
-1 amide bond absorption was observed. The main particle diameter of this polyamide particulate polymer is approximately 10 to 80 μm.
It was hot.
実施例 ７
(1) 分散安定剤の合成
実施例１、(1)と同様の装置を用いて、フラス
コにISOPAR−H1114ｇを入れ、120℃に昇温
した。窒素ガスを通しながら、あらかじめ調整
したラウリルメタクリレート1270ｇ、メタクリ
ル酸−２−ヒドロキシエチル104ｇ、メタクリ
ル酸グリシジル113.6ｇ、過酸化ベンゾイルペ
ースト70.3ｇの混合物をかくはんしながら２時
間かけて滴下した。引き続き140℃に昇温し、
同温度で４時間反応させた。この分散安定剤溶
液は170℃で２時間乾燥した時の不揮発分は41
重量％であり、分散安定剤の数平均分子量は
10000であつた。Example 7 (1) Synthesis of dispersion stabilizer Using the same apparatus as in Example 1 (1), 114 g of ISOPAR-H was placed in a flask and the temperature was raised to 120°C. While passing nitrogen gas, a mixture of 1270 g of lauryl methacrylate, 104 g of 2-hydroxyethyl methacrylate, 113.6 g of glycidyl methacrylate, and 70.3 g of benzoyl peroxide paste was added dropwise over 2 hours while stirring. Continue to raise the temperature to 140℃,
The reaction was continued at the same temperature for 4 hours. When this dispersion stabilizer solution was dried at 170℃ for 2 hours, the nonvolatile content was 41
% by weight, and the number average molecular weight of the dispersion stabilizer is
It was 10,000.
(2) 粒子状重合体の合成
実施例１、(2)と同じ装置を用いて、窒素ガス
を通しながらMR−100（４・4′−ジフエニルメ
タンジイソシアネート、トリフエニルメタン−
４・4′・4″−トリイソシアネート等の混合体、
イソシアネート基含有率31重量％、日本ポリウ
レタン工業社製、商品名）50.8ｇ(1)で得た分散
安定剤溶液19ｇ、ISOPAR−H150ｇを入れ、
かくはんしながら100℃昇温した。あらかじめ
微粉末化したトリメリツト酸無水物72ｇを添加
し、100℃で１時間、140℃で１時間、さらに
180℃に昇温して反応を進めた。ISOPAR−Ｈ
中に分散した黄色の粒子状重合体を得たので、
これを過によつて回収し、ｎ−ヘキサン、メ
タノールで精製したのち、減圧下、60℃で５時
間乾燥させた。この粒子状重合体の赤外吸収ス
ペクトルには1780cm-1にイミド結合、1650cm-1
と1540cm-1にアミド結合の吸収が認められた。
このポリアミドイミド粒子状重合体の主粒子径
は約20〜30μｍであつた。(2) Synthesis of particulate polymer Using the same equipment as in Example 1 and (2), MR-100 (4,4'-diphenylmethane diisocyanate, triphenylmethane-
Mixtures of 4, 4′, 4″-triisocyanates, etc.
Add 19 g of the dispersion stabilizer solution obtained from Isocyanate group content 31% by weight, manufactured by Nippon Polyurethane Kogyo Co., Ltd. (trade name) 50.8 g (1) and 150 g of ISOPAR-H,
The temperature was raised to 100°C while stirring. Add 72 g of trimellitic anhydride, which has been finely powdered in advance, and heat at 100°C for 1 hour, then at 140°C for 1 hour, and then
The reaction was proceeded by raising the temperature to 180°C. ISOPAR-H
Now that we have obtained a yellow particulate polymer dispersed in
This was collected by filtration, purified with n-hexane and methanol, and then dried at 60° C. for 5 hours under reduced pressure. The infrared absorption spectrum of this particulate polymer includes an imide bond at 1780 cm -1 and an imide bond at 1650 cm -1.
An amide bond absorption was observed at 1540 cm -1 .
The main particle diameter of this polyamide-imide particulate polymer was about 20 to 30 μm.
実施例 ８
４・4′−ジフエニルメタンジイソシアネート
257.1ｇ、トリメリツト酸無水物246.9ｇ、
ISOPAR−H514.3ｇ及び実施例４、(1)で得た分散
安定剤溶液68.6ｇを混合してホモミキサーを使用
して高速かく拌に100℃１時間反応を進めた。そ
の後、実施例１、(2)と同様の装置に移し、140℃
で１時間、180℃に昇温して４時間反応を進め、
反応終了後ｎ−ヘキサン、メタノールで精製し乾
燥した。得られた粒子状重合体の赤外吸収スペク
トルには1780cm-1にイミド結合、1650cm-1と1540
cm-1にアミド結合の吸収が認められた。このポリ
イミド粒子状重合体の主粒子径は約0.5〜２μで
あつた。Example 8 4,4'-diphenylmethane diisocyanate
257.1g, trimellitic anhydride 246.9g,
14.3 g of ISOPAR-H and 68.6 g of the dispersion stabilizer solution obtained in Example 4 (1) were mixed, and the reaction was proceeded for 1 hour at 100° C. with high speed stirring using a homomixer. Thereafter, it was transferred to the same apparatus as in Example 1, (2), and heated to 140°C.
for 1 hour, then raise the temperature to 180℃ and proceed with the reaction for 4 hours.
After the reaction was completed, it was purified with n-hexane and methanol and dried. The infrared absorption spectrum of the obtained particulate polymer shows an imide bond at 1780 cm -1 and an imide bond at 1650 cm -1 and 1540 cm -1.
Absorption of amide bond was observed at cm -1 . The main particle diameter of this polyimide particulate polymer was about 0.5 to 2 microns.
Claims (1)
非水有機液体及び非水有機液体に可溶な分散安定
剤の存在下で、ポリイソシアネート（）と酸無
水物基を有するポリカルボン酸（）及び／又は
ポリカルボン酸（）とを反応させて非水有機液
体中に分散された粒子状重合体とすることを特徴
とする粒子状重合体の製造法。 ２ 分散安定剤がラウリルメタクリレート、ステ
アリルメタクリレート、ラウリルアクリレート又
はステアリルアクリレートとメタクリル酸−２−
ヒドロキシエチル、メタクリル酸グリシジル、ア
クリル酸−２−ヒドロキシエチル及び／又はアク
リル酸グリシジルとのランダム共重合体である特
許請求の範囲第１項記載の粒子状重合体の製造
法。 ３ 非水有機液体が脂肪族又は脂環族炭化水素で
ある特許請求の範囲第１項又は第２項記載の粒子
状重合体の製造法。 ４ ポリイソシアネート（）が４・4′−ジフエ
ニルメタンジイソシアネート、４・4′−ジフエニ
ルエーテルジイソシアネート、トリレンジイソシ
アネート、トリフエニルメタン−４・4′・4″−ト
リイソシアネート又はイソシアヌレート環を有す
るポリイソシアネートである特許請求の範囲第１
項、第２項又は第３項記載の粒子状重合体の製造
法。 ５ 酸無水物基を有するポリカルボン酸（）が
トリメリツト酸無水物、ピロメリツト酸二無水
物、３・3′・４・4′−ベンゾフエノンテトラカル
ボン酸二無水物又は２・２−ビス〔４−（３・４
−ジカルボキシフエノキシ）フエニル〕プロパン
二無水物である特許請求の範囲第１項、第２項、
第３項又は第４項記載の粒子状重合体の製造法。 ６ ポリカルボン酸がイソフタル酸、テレフタル
酸、トリメシン酸、トリス（２−カルボキシエチ
ル）イソシアヌレート又はニトリロ三酢酸である
特許請求の範囲第１項、第２項、第３項、第４項
又は第５項記載の粒子状重合体の製造法。[Claims] 1. Polyisocyanate () and acid anhydride groups are combined in the presence of a non-aqueous organic liquid that is insoluble in the particulate polymer to be produced and a dispersion stabilizer that is soluble in the non-aqueous organic liquid. 1. A method for producing a particulate polymer, which comprises reacting a polycarboxylic acid () and/or a polycarboxylic acid () having a particulate polymer dispersed in a non-aqueous organic liquid. 2 The dispersion stabilizer is lauryl methacrylate, stearyl methacrylate, lauryl acrylate, or stearyl acrylate and methacrylic acid-2-
A method for producing a particulate polymer according to claim 1, which is a random copolymer with hydroxyethyl, glycidyl methacrylate, 2-hydroxyethyl acrylate and/or glycidyl acrylate. 3. The method for producing a particulate polymer according to claim 1 or 2, wherein the non-aqueous organic liquid is an aliphatic or alicyclic hydrocarbon. 4 Polyisocyanate () has 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, tolylene diisocyanate, triphenylmethane-4,4',4''-triisocyanate or isocyanurate ring Claim 1 which is polyisocyanate
A method for producing a particulate polymer according to item 1, 2 or 3. 5 Polycarboxylic acid () having an acid anhydride group is trimellitic anhydride, pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, or 2,2-bis[ 4-(3・4
-dicarboxyphenoxy)phenyl]propane dianhydride, claims 1 and 2;
A method for producing a particulate polymer according to item 3 or 4. 6. Claims 1, 2, 3, 4 or 6, wherein the polycarboxylic acid is isophthalic acid, terephthalic acid, trimesic acid, tris(2-carboxyethyl)isocyanurate or nitrilotriacetic acid. A method for producing a particulate polymer according to item 5.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58148665A JPS6040114A (en) | 1983-08-12 | 1983-08-12 | Preparation of granular polymer |
| EP84109502A EP0137205A3 (en) | 1983-08-12 | 1984-08-09 | Process for producing particulate polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58148665A JPS6040114A (en) | 1983-08-12 | 1983-08-12 | Preparation of granular polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6040114A JPS6040114A (en) | 1985-03-02 |
| JPS6220215B2 true JPS6220215B2 (en) | 1987-05-06 |
Family
ID=15457875
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58148665A Granted JPS6040114A (en) | 1983-08-12 | 1983-08-12 | Preparation of granular polymer |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0137205A3 (en) |
| JP (1) | JPS6040114A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4855164A (en) * | 1988-02-12 | 1989-08-08 | Ppg Industries, Inc. | Stable multiphase coating compositions |
| JP2594117B2 (en) * | 1988-06-27 | 1997-03-26 | 日本ポリウレタン工業 株式会社 | Method for producing polyurethane polymer gel |
| AT392974B (en) * | 1989-07-13 | 1991-07-25 | Chemiefaser Lenzing Ag | MIXED POLYIMIDES AND METHOD FOR THE PRODUCTION THEREOF |
| FR2731431A1 (en) * | 1995-03-09 | 1996-09-13 | Protex Manuf Prod Chimiq | Thermosetting compsns. used in forming films with low water vapour permeability |
| US20130102753A1 (en) * | 2011-10-25 | 2013-04-25 | Fujifilm Hunt Chemicals, Inc. | Low residual solvent polyamideimide powder from suspension polymerization |
| CN105017533A (en) * | 2015-07-03 | 2015-11-04 | 东华大学 | Preparation method for polyamide imide coating |
| JP6930110B2 (en) * | 2017-01-16 | 2021-09-01 | 荒川化学工業株式会社 | Thermosetting release coating agent, release film and its manufacturing method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4032516A (en) * | 1973-05-09 | 1977-06-28 | Usm Corporation | Method of making polyurethane powder |
| US4156065A (en) * | 1977-01-21 | 1979-05-22 | The Upjohn Company | Catalytic condensation of isocyanates and carboxylic acids or anhydrides |
| US4427822A (en) * | 1982-02-15 | 1984-01-24 | Hitachi Chemical Co., Ltd. | Process for producing particulate polymer having imide groups |
-
1983
- 1983-08-12 JP JP58148665A patent/JPS6040114A/en active Granted
-
1984
- 1984-08-09 EP EP84109502A patent/EP0137205A3/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6040114A (en) | 1985-03-02 |
| EP0137205A3 (en) | 1986-06-11 |
| EP0137205A2 (en) | 1985-04-17 |
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